Användningen av biobränslen har ökat för att minska utsläppen från fossila bränslen. Biobränslen kan dock leda till beläggningar inuti injektorn, vilka påverkar fordonets  körbarhet. Den mest trodda hypotesen bakom beläggningsbildningen är att förorening av motorolja i bränslesystemet leder till bildning av kalciumsulfatkristaller som mjuka partiklar fäster till. Dessutom påstås det att temperaturen har en signifikant påverkan på beläggningsbildningen. För att ställa om till mer förnyelsebara bränslen krävs mer förståelse bakom beläggningarnas mekanism. Därför var syftet med denna studie att undersöka mekanismen bakom interna injektorbeläggningar med en nydesignad rigg i laboratorieskala för att få en djupare förståelse av mekanismen, och i synnerhet rollen av kalciumsulfat och temperatur. Syftet uppnåddes genom att dela upp det experimentella arbetet i två delar:a) Köra riggen med testbränslen följt av analyser av de körda proverna med huvudsakligen SEM-EDX och FTIR, för att förstå rollen av temperatur och motorolja för beläggningarnas mekanism. b) Löslighetsstudier av kalciumsulfat för att förstå rollen av kalciumsulfat för beläggningarnas mekanism. Resultaten visade att den nydesignade testriggen fungerade bra med resultat som överensstämde med litteratur och erbjöd repeterbarhet. Därmed rekommenderas riggen för framtida studier av interna injektorbeläggningar. En djupare förståelse av mekanismen bakom interna injektorbeläggningar uppnåddes framgångsrikt. För första gången utfördes en FTIR och SEM-EDX studie över en temperaturgradient, vilket gjorde det möjligt att se starttemperaturen för olika reaktioner och identifiera beläggningar i olika temperaturintervall. Det visades att beläggningsbildningen var temperaturberoende med olika typer av beläggningar i olika temperaturintervall. Vid temperaturer under 100°C var zinksulfat och oreagerat metallkarboxylat de dominanta ämnena. Över 100°C ändrade metallkarboxylatet form och blev mer koncentrerat medan koncentrationen av zinksulfat minskade. Dessutom visades det att kalciumsulfat bildades i stor utsträckning när temperaturen översteg 100°C. Temperaturstudien och resultaten är unika och okända i litteraturen. Ostwald-mognad har föreslagits som en möjlig mekanism i litteraturen men visade sig vara osannolik. Upplösningen av kalciumsulfat av motoroljans additiv följt av utfällning i bränslet visade sig vara en mer sannolik mekanism. Det visades också att tvålbeläggningar främjade beläggningsbildning av kalciumsulfatkristaller, vilket överensstämmer med fältobservationer då de vanligtvis samexisterar. / The use of biofuels has increased to reduce the emissions from fossil fuels. However, the use of biofuels results in deposit formation inside the injector, which leads to issues with the drivability of the vehicle. The most believed hypothesis behind the deposit formation is that engine oil contamination in the fuel system leads to formation of calcium sulphate crystals that soft particles adhere to. Moreover, temperature is claimed to have a significant effect on the deposit formation. To ease the shift towards more renewable fuels, more understanding behind the deposit mechanism is needed. Therefore, this study aimed to investigate the mechanism behind internal injector deposits with a newly designed lab scale rig to get a deeper understanding of the mechanism, and especially the role of calcium sulphate and temperature. The aim was achieved by dividing the experimental work into two parts:a) Running the test-rig with test fuels followed by analyses of the samples with mainly SEM-EDX and FTIR, to understand the role of temperature, and engine oil for the deposit mechanism. b) Solubility studies of calcium sulphate to understand the role of calcium sulphate for the deposit mechanism. The results showed that the newly designed test rig worked well, where the results were consistent with literatureand offered repeatability. Thereby, the rig is recommended for future studies of internal injector deposits. A deeper understanding of the mechanism behind the internal injector deposits was successfully achieved. For the first time, a FTIR and SEM-EDX study was performed over a temperature gradient, which made it possible to see the onset temperature for different reactions and to identify deposits in different temperature ranges. It was showed that the deposit formation was temperature dependent with different types of deposits in different temperature ranges. At temperatures below 100°C, zinc sulphate and unreacted metal carboxylates were the dominant species. Above 100°C, the metal carboxylates changed form and became more concentrated while the concentration of zinc sulphate decreased. Moreover, calcium sulphate showed to be formed to a large extent when the temperature exceeded 100°C. The temperature study and results are unique and unknown in the literature. Ostwald ripening has been proposed as a possible mechanism in the literature but turned out to be unlikely. The dissolution of calcium sulphate by engine oil additives followed by precipitation in the fuel showed to be a more likely mechanism. It was also shown that soap deposits promoted the deposit formation of calcium sulphate crystals, which is in line with the field observations since they normally coexist.

Turbine engine efficiency modeling depends on many parameters related to fluid dynamics and heat transfer. Many of these parameters change dynamically once the engine enters service and begins to experience surface degradation. This thesis presents a validation of the design and operation of an accelerated testing facility for the study of foreign deposit layers typical to the operation of land-based gas turbines. It also reports on the use of this facility in an effort to characterize the change in thermal resistance on the surface of turbine blades as deposits accumulate. The facility was designed to produce turbine deposits in a 4-hour test that would simulate 10,000 hours of turbine operation. This is accomplished by matching the net foreign particulate throughput of an actual gas turbine. Flow Mach number, temperature and particulate impingement angle are also matched. Validation tests were conducted to model the ingestion of foreign particulate typically found in the urban environment. The majority of this particulate is ceramic in nature and smaller than 10µm in size, but varies in size up to 80µm. Deposits were formed for flow Mach number and temperature of 0.3 and 1150°C respectively, using air plasma sprayed (APS) thermal barrier coat (TBC) material coupons donated from industry. These conditions are typical of a modern, first stage nozzle. Investigations over a range of impingement angles yielded samples with deposit thicknesses from 50 to 200µm in 4-hour, accelerated-service simulations. Above a threshold temperature, deposit thickness was dependent primarily upon particle concentration. Test validation was achieved using direct comparison with deposits from service hardware. Deposit characteristics affecting blade heat transfer via convection and conduction were assessed. Surface topography analysis indicated that the surface structure of the generated deposits were similar to those found on actual turbine blades. Scanning electron microscope (SEM) and x-ray spectroscopy analyses indicated that the deposit microstructures and chemical compositions were comparable to turbine blade deposit samples obtained from industry. A roadmap for the development of a theoretical model of thermal resistance using the SEM scan is presented. Thermal resistance experiments conducted with deposit samples indicate that a general decrease in thermal resistance occurs as the samples are exposed to operating conditions in the accelerated testing facility. This is likely due to sintering effects within the TBC dominating any thermal resistance increase arising from deposition. Recommendations for future research into the interaction between TBC sintering and deposit evolution are presented.

The development of thermal barrier coatings (TBCs) has been undoubtedly the most critical advancement in materials technology for modern gas turbine engines. TBCs are widely used in gas turbine engines for both power-generation and propulsion applications. Metallic oxidation-resistant coatings (ORCs) are also widely employed as a stand-alone protective coating or bond coat for TBCs in many high-temperature applications. Among the widely studied durability issues in these high-temperature protective coatings, one critical challenge that received greater attention in recent years is their resistance to high-temperature degradation due to corrosive deposits arising from fuel impurities and CMAS (calcium-magnesium-alumino-silicate) sand deposits from air ingestion. The presence of vanadium, sulfur, phosphorus, sodium and calcium impurities in alternative fuels warrants a clear understanding of high-temperature materials degradation for the development of fuel-flexible gas turbine engines. Degradation due to CMAS is a critical problem for gas turbine components operating in a dust-laden environment. In this study, high-temperature degradation due to aggressive deposits such as V2O5, P2O5, Na2SO4, NaVO3, CaSO4 and a laboratory-synthesized CMAS sand for free-standing air plasma sprayed (APS) yttria stabilized zirconia (YSZ), the topcoat of the TBC system, and APS CoNiCrAlY, the bond coat of the TBC system or a stand-alone ORC, is examined. Phase transformations and microstructural development were examined by using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. This study demonstrated that the V2O5 melt degrades the APS YSZ through the formation of ZrV2O7 and YVO4 at temperatures below 747°C and above 747°C, respectively. Formation of YVO4 leads to the depletion of the Y2O3 stabilizer and the deleterious transformation of the YSZ to the monoclinic ZrO2 phase. The investigation on the YSZ degradation by Na2SO4 and a Na2SO4 + V2O5 mixture (50-50 mol. %) demonstrated that Na2SO4 itself did not degrade the YSZ, however, in the presence of V2O5, Na2SO4 formed vanadates such as NaVO3 that degraded the YSZ through YVO4 formation at temperature as low as 700°C. The APS YSZ was found to react with the P2O5 melt by forming ZrP2O7 at all temperatures. This interaction led to the depletion of ZrO2 in the YSZ (i.e., enrichment of Y2O3 in t' -YSZ) and promoted the formation of the fluorite-cubic ZrO2 phase. Above 1250°C, CMAS deposits were observed to readily infiltrate and significantly dissolve the YSZ coating via thermochemical interactions. Upon cooling, zirconia reprecipitated with a spherical morphology and a composition that depended on the local melt chemistry. The molten CMAS attack destabilized the YSZ through the detrimental phase transformation (t - > t - > f + m). Free standing APS CoNiCrAlY was also prone to degradation by corrosive molten deposits. The V2O5 melt degraded the APS CoNiCrAlY through various reactions involving acidic dissolution of the protective oxide scale, which yielded substitutional-solid solution vanadates such as (Co,Ni)3(VO4)2 and (Cr,Al)VO4. The molten P2O5, on the other hand, was found to consume the bond coat constituents significantly via reactions that formed both Ni/Co rich phosphates and Cr/Al rich phosphates. Sulfate deposits such as Na2SO4, when tested in encapsulation, damaged the CoNiCrAlY by Type I acidic fluxing hot corrosion mechanisms at 1000°C that resulted in accelerated oxidation and sulfidation. The formation of a protective continuous Al2O3 oxide scale by preoxidation treatment significantly delayed the hot corrosion of CoNiCrAlY by sulfates. However, CoNiCrAlY in both as-sprayed and preoxidized condition suffered a significant damage by CaSO4 deposits via a basic fluxing mechanism that yielded CaCrO4 and CaAl2O4. The CMAS melt also dissolved the protective Al2O3 oxide scale developed on CoNiCrAlY by forming anorthite platelets and spinel oxides. Based on the detailed investigation on degradation of the APS YSZ and CoNiCrAlY by various corrosive deposits, an experimental attempt was carried out to mitigate the melt-induced deposit attack. Experimental results from this study demonstrate, for the first time, that an oxide overlay produced by electrophoretic deposition (EPD) can effectively perform as an environmental barrier overlay for APS TBCs. The EPD protective overlay has a uniform and easily-controllable thickness, uniformly distributed closed pores and tailored chemistry. The EPD Al2O3 and MgO overlays were successful in protecting the APS YSZ TBCs against CMAS attack and hot corrosion attack (e.g., sulfate and vanadate), respectively. Furnace thermal cyclic oxidation testing of overlay-modified TBCs on bond-coated superalloy also demonstrated the good adhesive durability of the EPD Al2O3 overlay.

No description available.

[pt] A extinta mineradora Cia. Mercantil e Industrial Ingá era responsável por grande parte da produção de zinco no país. Após decretada sua falência, em 1998, sua área permaneceu abandonada por mais de 10 anos. Durante essa década, insumos e resíduos foram armazenados e dispostos de forma inadequada, gerando um dos maiores passivos ambientais já vistos no estado do Rio de Janeiro. Sua barragem de rejeito, construída sem qualquer impermeabilização de base, continha aproximadamente 430.000 m3 de efluente com altas concentrações de zinco (824 mg/l) e cádmio (2,9 mg/l). Além do risco de contaminação das águas subterrâneas, a possibilidade de ruptura do dique desta barragem era cada vez mais evidente, principalmente durante as temporadas de chuva. Em 2004, a PUC-Rio foi contrada pela Massa Falida para assumir a área e propor medidas emergenciais para a remediação do passivo ambiental. Em 2008, a universidade desenvolveu um sistema de tratamento de efluente líquido, que conseguiu aumentar o volume tratado por mês, passando de 24.000 m3/mês para 160.000 m3/mês, eliminando o risco de ruptura do dique. O sucesso desse sistema deu origem a este trabalho. O propósito desta dissertação foi desenvolver o conceito do sistema utilizado na remediação ambiental da Cia. Mercantil e Industrial Ingá, dando origem a um projeto piloto compacto e eficiente, capaz de se adequar a diferentes tipos de efluentes. / [en] After bankruptcy in 1998, a major Brazilian zinc producer – Cia. Mercantil e Industrial Ingá – industrial site was abandoned for about ten years. As a result, raw materials and industrial waste were disposed in an inappropriate way for one decade, creating one of the biggest environmental liabilities in the State of Rio de Janeiro – Brazil. The company s waste dam contained around 430.000 m3 of effluent with high concentrations of zinc (824 mg/l) and cadmium (2,9 mg/l), even though it was not conveniently sealed. Besides de risk of contamination of underground reservoirs of water, the possibility of a dam breakdown became evident, especially during the raining seasons. In 2004, the Catholic University of Rio de Janeiro (PUC-Rio) was hired by the authority Massa Falida – legally responsible for managing the assets and liabilities of the bankrupted company – to propose urgent measures to repair the environmental damages caused by the mining company. In 2008, The Catholic University team developed a liquid effluent treatment system which increased the previous treatment capacity from 24.000 m3/month to 160.000 m3 /month. This increase eliminates any risk of a dam breakdown. Based on this important achievement, the present work intends to develop and systematize the conceptual approach applied to the Cia. Mercantil e Industrial Ingá case, in order to give birth to a compact e efficient pilot project, capable to be adjusted to different types of effluents.

No abstract provided. / Thesis / Master of Engineering (MEngr) / Scope and contents: This thesis describes the behaviour of iron ore-water suspensions under turbulent flow conditions. This work is divided into two parts. Part I deals with the regimes of transport under steady state flow conditions in circular and horizontal ducts. The heterogeneous flow regime is extensively analyzed; a sequential discrimination of models with an oriented design of experiments have permitted the determination of the best model to correlate hydraulic gradients for these suspensions. A critical discussion on the limit deposit conditions is also included. Part II describes the behaviour of clear water under oscillatory flow conditions. The study demonstrates that the quasi-steady state hypothesis, i.e., fully developed flow assumption, applied to pulsatile turbulent flow under the conditions studied. Observations on the behaviour of iron ore-water suspensions under pulsatile flow are also included. The experiments were carried out using a new air-pulsing technique.

<p> The recent discovery of ore grade gold in the Hemlo area of Northern Ontario has provided the initiative for extensive exploration in that region. This study concentrates on rocks from the footwall to the ore zone on the Williams property of Long Lac Mineral Exploration. </p> <p> The footwall rocks consist of fine grained, finely laminated tuffs. The suite has undergone low grade regional metamorphism. Retrograde metamorphic effects are also present but appear to be confined to certain bands. Some of the minerals may have been introduced by the action of metasomatic fluids. </p> <p> The tuffs are quite felsic and many have the composition of a rhyolite. Samples tested for gold have up to 200 times the background concentration of a rhyolite . The gold is associated with high Sio2 and K20 and low Al2O3, CaO, Na2O, Fe2O3 and MgO contents. </p> <p> The ore deposit is similar in many respects to the Bousquet deposit of Northern Quebec. The Bousquet deposit has been interpreted as syngenetic by some authors and therefore it is quite possible that the Hemlo deposit is syngenetic as well. However the metamorphism and possible metasomatism that these rocks have undergone suggests that it may be an epigenetic deposit. Due to the limited number of samples in this study it could not conclusively be determined which hypothesis is correct. </p> / Thesis / Bachelor of Science (BSc)

Данная работа посвящена одному из самых интересных финансовых рынков- рынку сберегательных продуктов. Его уникальность обусловлена уровнем масштабирования и вовлеченности широких слоев населения. А современное состояние характеризуется синергетическим объединением традиционных и инновационных составляющих. Отталкиваясь от ракурса исторического развития сберегательного дела на примере СБ РФ, автор подробно рассматривает все виды сберегательных продуктов с учетом их особенностей. Проводит эмпирический анализ объема вкладов, предлагает методологию оценки сбережений. На базе проведенных оценок, сформированы предложения по дополнению продуктового ряда, а, так же, обозначен основной вектор роста сбережений- дальнейшее расширение технологических и инновационных возможностей и сервисов. / This work is devoted to one of the most interesting financial markets - the market of savings products. Its uniqueness is due to the level of scaling and involvement of the general population. And the current state is characterized by a synergetic combination of traditional and innovative components. Starting from the perspective of the historical development of the savings business using the example of the Sberbank of Russia, the author examines in detail all types of savings products, taking into account their characteristics. The author conducts an empirical analysis of the volume of deposits, offers a methodology for estimating savings. Based on the evaluations the proposals to supplement the product range were made. The main vector of savings growth was also identified – the further expansion of technological and innovative capabilities and services.

Die Umsetzung einer effektiven Klimapolitik ermöglicht die Verringerung von Treibhausgasemissionen und damit die Eindämmung des Klimawandels. Eine solche Politik hat jedoch negative Auswirkungen auf die direkt oder indirekt in der fossilen Industrie tätigen Akteure, wenn deren Vermögensgegenstände wertlos werden (auch „Asset Stranding“ genannt). Diese Arbeit leistet einen Beitrag zum Verständnis der Wechselwirkung zwischen Klimapolitik und Asset Stranding: Sie untersucht angebotsseitige Politikmaßnahmen in der fossilen Brennstoffindustrie, das Ausmaß und die Verteilung von Asset Stranding auf Ebene der Anlagenbesitzer im Energiesektor und die Wechselwirkungen zwischen Asset Stranding, Erwartungen über Klimapolitik und systemischen Finanzkrisen. Darüber hinaus gibt die Arbeit einen Überblick über die Literatur im Bereich Klimaökonomie zu Asset Stranding und zu entgangenen Gewinnen der Produzenten fossiler Brennstoffe aufgrund von Klimapolitik. Die Arbeit besteht aus fünf Artikeln (Kapitel 2-6), die von einer allgemeinen Einleitung und einer Schlussfolgerung umschlossen werden. / The implementation of effective climate policies facilitates reducing greenhouse gas emissions and thereby mitigating climate change. Such policies, however, have adverse effects on stakeholders directly or indirectly engaged in the fossil industry if they find the value of their assets "stranded". This thesis contributes to our understanding of the interaction between climate policies and asset stranding: It studies supply-side policies in the upstream fossil fuel extraction industry, the extent and distribution of stranded assets at the asset owner level in the power sector, and the interaction of asset stranding, expectations of climate policies, and financial systemic crises. Further, the thesis surveys the climate economics literature on stranded assets and fossil fuel producers' lost profits due to climate policies. The thesis is a compilation of five articles (Chapters 2-6) encased by a general introduction and a conclusion.

Diese Dissertation besteht aus drei Aufsätzen, die die Rolle unterschiedlichester Arten von finanziellen Friktionen sowohl auf Firmenseite, als auch auf Bankenseite, für die Übertragung von finanziellen Schocks und Geldpolitik analysieren. Im ersten Aufsatz, "Firm Heterogeneity and the Capital Market", studiere ich welche Art von Finanzbeschränkungen der Firmen für die Übertragung von Kapitalmarktfinanzierungsschocks, als auch geldpolitischen Schocks, ausschlaggebend sind. Hierbei gehöre ich zu den Ersten in der Literatur, die Kapitalmarktfinanzierungsschocks direkt aus Firmendaten schätzen. Ich zeige in meiner Studie, dass es für ein tieferes Verständnis von Firmeninvestitionen entscheidend ist, zwischen verschiedenen potentiellen Maßzahlen für Finanzbeschränkungen der Firmen zu unterscheiden. Konkret zeige ich, dass finanzbeschränkte Firmen mit hohen erwarteten zukünftigen Gewinnen nach einem Kapitalmarktfinanzierungsschock ihre Investitionen stärker als andere Firmen erhöhen. Im Unterschied dazu, spielt für die Übertragung von Geldpolitik auf Firmeninvestitionen die Liquidität und die Verschuldungsquote eine stärkere Rolle. Diese Resultate implizieren, dass für Politikmaßnahmen die eine Erhöhung von gesamtwirtschaftlichen Investitionen zum Ziel haben, sowohl Geldpolitik als auch der Zugang zum Kapitalmarkt im Blick behalten werden muss. Der zweite Aufsatz, "The Macroeconomic Effects of a European Deposit (Re-)Insurance Scheme", wurde gemeinsam mit Marius Clemens und Stefan Gebauer geschrieben. Hier analysieren wir die Wohlfahrts- und Stabilisierungseffekte einer europäischen Einlagenrückversicherung. Unser Regime-Switching-Zwei-Länder-DSGE-Modell impliziert, dass eine europäischer Einlagenrückversicherungsfond Konjunkturschwankungen in beiden Ländern gut ausgleichen kann und die Risikoteilung zwischen beiden Ländern verbessert. Allerdings kann das Wirtschaftswachstum langfristig leiden, wenn die Einzahlungen der Banken in den jeweiligen Ländern in die europäische Einlagenversicherung schlecht gelöst sind. Im dritten Aufsatz, "The Financial Accelerator, Wages and Optimal Monetary Policy", analysiere ich in einem makroökonomischen Modell, welche Rolle Geldpolitik einnehmen sollte, wenn Friktionen auf der Bankenseite und Lohnrigiditäten existieren. Ich zeige, dass Zentralbanken im Fall von Finanzmarktschocks einen großen Fokus auf die Stabilisierung von Lohninflation legen sollten. Dies erklärt sich über die geringere Sensitivität von Kapitalnachfrage auf Änderungen in Reallöhnen im Falle von Friktionen auf dem Bankenmarkt. Höhere Reallöhne führen zudem zu Inflation und einem niedrigeren Risikoaufschlag auf Firmenkredite. / This thesis consists of three essays that focus on the role of heterogeneity in both the type and the degree of financial frictions for the pass-through of financial shocks and of monetary policy. In the first essay, "Firm Heterogeneity and the Capital Market", I investigate the importance of firms' financial constraints for the transmission of both equity shocks and monetary policy shocks. I am the first in the literature to obtain an instrument to equity financing shocks directly from firm-level data. I show in my study, that it is necessary to strictly distinguish between different forms of financial constraints if researchers want to investigate the role of firm heterogeneity on firm investment rates. In particular, financially constrained firms with high expected future profits increase their investment rate relatively more when capital market funding conditions are improved. In contrast, firm liquidity and high debt burden of firms explain the heterogeneity in firms' investment response to monetary policy. Therefore, policy makers have to consider both monetary policy conditions and access of firms to capital markets in order to relax the firms' financial constraints and to stimulate investment. The second essay, "The Macroeconomic Effects of a European Deposit (Re-) Insurance Scheme", is joint work with Marius Clemens and Stefan Gebauer. We analyze the stabilization effects of a common European deposit re-insurance scheme. To this end we build a two-country regime-switching general equilibrium model. The findings suggest that a common European deposit insurance scheme reduces business cycle fluctuations in both countries and improve risk sharing within the union. Long term macroeconomic performance however can deteriorate when contributions to the deposit insurance are non-deductible and designed poorly. In the third essay, "The Financial Accelerator, Wages and Optimal Monetary Policy", I investigate optimal monetary policy under the existence of both banking frictions and wage rigidities. In my macroeconomic model, I document that after the economy is hit by adverse financial shocks, monetary policy should stabilize wage inflation to improve welfare. This result can be explained as follows: The presence of financial frictions makes capital demand less elastic to changes in real wages. The wage-inflation stabilization regime that results in relatively higher real wages reduces the capital demand by less in comparison to the non-financial-friction economy. Higher real wages increase inflation and lowers the credit spread.