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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
91

Convers?o catal?tica de clorometano em hidrocarbonetos

Rojas, Leopoldo Oswaldo Alcazar 02 March 2012 (has links)
Made available in DSpace on 2014-12-17T15:01:54Z (GMT). No. of bitstreams: 1 LeopoldoOAR_TESE.pdf: 2477409 bytes, checksum: 8a0937fc273e62c20239012357028d11 (MD5) Previous issue date: 2012-03-02 / Amorphous silica-alumina and modified by incipient impregnation of iron, nickel, zinc and chromium were synthetized in oxide and metal state and evaluated as catalysts for the chloromethane conversion reaction. With known techniques their textural properties were determined and dynamics techniques in programmed temperature were used to find the acid properties of the materials. A thermodynamic model was used to determine the adsorption and desorption capacity of chloromethane. Two types of reactions were studied. Firstly the chloromethane was catalytically converted to hydrocarbons (T = 300 450 oC e m = 300 mg) in a fixed bed reactor with controlled pressure and flow. Secondly the deactivation of the unmodified support was studied (at 300 ?C and m=250 g) in a micro-adsorver provided of gravimetric monitoring. The metal content (2,5%) and the chloromethane percent of the reagent mixture (10% chloromethane in nitrogen) were fixed for all the tests. From the results the chloromethane conversion and selectivity of the gaseous products (H2, CH4, C3 and C4) were determined as well as the energy of desorption (75,2 KJ/mol for Ni/Al2O3-SiO2 to 684 KJ/mol for the Zn/Al2O3-SiO2 catalyst) considering the desorption rate as a temperature function. The presence of a metal on the support showed to have an important significance in the chloromethane condensation. The oxide class catalyst presented a better performance toward the production of hydrocarbons. Especial mention to the ZnO/Al2O3-SiO2 that, in a gas phase basis, produced C3 83 % max. and C4 63% max., respectively, in the temperature of 450 oC and 20 hours on stream. Hydrogen was produced exclusively in the FeO/Al2O3-SiO2 catalysts (15 % max., T = 550 oC and 5,6 h on stream) and Ni/SiO2-Al2O3 (75 % max., T = 400 oC and 21,6 h on stream). All the catalysts produced methane (10 ? 92 %), except for Ni/Al2O3-SiO2 and CrO/Al2O3-SiO2. In the deactivation study two models were proposed: The parallel model, where the product production competes with coke formation; and the sequential model, where the coke formation competes with the product desorption dessorption step. With the mass balance equations and the mechanism proposed six parameters were determined. Two kinetic parameters: the hydrocarbon formation constant, 8,46 10-4 min-1, the coke formation, 1,46 10-1 min-1; three thermodynamic constants (the global, 0,003, the chloromethane adsorption 0,417 bar-1, the hydrocarbon adsorption 2,266 bar-1), and the activity exponent of the coke formation (1,516). The model was reasonable well fitted and presented a satisfactory behavior in relation with the proposed mechanism / S?lica alumina amorfa e modificada por impregna??o incipiente de precursores de ferro, n?quel, zinco e cromo foram sintetizados na forma de ?xido e reduzidos, tendo sido posteriormente avaliados como catalisadores na convers?o de clorometano em hidrocarbonetos. Propriedades texturais e t?cnicas din?micas em temperatura programada foram usadas para a determina??o das propriedades ?cidas dos materiais. Um modelo termodin?mico para representar a capacidade de adsor??o e dessor??o de clorometano foi avaliado. Dois tipos de rea??es foram abordados. No primeiro, o clorometano foi convertido cataliticamente a hidrocarbonetos (T = 300 450 oC e m = 300 mg) em um reator de leito fixo catal?tico com controle de fluxo, press?o e vaz?o m?ssica e, no segundo, com o suporte puro (T = 300 oC e m = 250 mg) foi estudado a rea??o de desativa??o do catalisador pelo coque em um micro adsorvedor com monitoramento gravim?trico. O teor de metal no suporte (2,5 %) e o percentual de clorometano na mistura (10 %) foram mantidos constantes durante os experimentos. Com os resultados obtidos foram avaliadas a convers?o e a seletividade dos produtos gasosos, ou seja, H2, CH4, C3 e C4 bem como a energia da etapa de dessor??o (75,2 KJ/mol para o Ni/Al2O3-SiO2 e 684 KJ/mol para o catalisador Zn/Al2O3-SiO2), considerando a taxa de adsor??o do g?s em fun??o da temperatura. A presen?a do metal no suporte mostrou uma import?ncia significativa em termos de atividade na rea??o de condensa??o do clorometano. Os catalisadores na forma de ?xido apresentaram melhor desempenho para obten??o de hidrocarbonetos. ? poss?vel destacar o ZnO/Al2O3-SiO2 que , em termos de constituinte gasoso, produziu apenas C3 (M?x. de 83 %) e C4 (M?x. de 63%), respectivamente, na temperatura de 450 oC e 20 horas de rea??o,. O g?s hidrog?nio foi formado exclusivamente com os catalisadores FeO/Al2O3-SiO2 (M?x. de 15 %, T = 550 oC e tempo de rea??o de 5,6 h) e Ni/SiO2-Al2O3 (M?x. 75 %, T = 400 oC e tempo de rea??o de 21,6 h). Todos os catalisadores produziram o g?s metano (10 ? 92 %), salvo os do tipo Ni/Al2O3- SiO2 e CrO/Al2O3-SiO2. No estudo com o suporte puro foram propostos dois modelos de iii desativa??o, do tipo paralelo, onde a forma??o do produto compete com a forma??o de coque e o sequencial, onde a etapa de dessor??o ? a competidora. Com as equa??es do balan?o de massa baseadas no mecanismo proposto foram determinados duas constantes cin?ticas (a primeira de valor 8,01?10-4 min-1, relacionada ? etapa da forma??o de hidrocarbonetos e a segunda, 1,46?10-1 min-1, ao coque depositado no s?tio do material), tr?s constantes de equil?brio (a global 0,003, relativa ao clorometano 0,417 bar-1, e a de forma??o de hidrocarbonetos 2,266 bar-1) e o do perfil do fator de atividade (1,516). Em termos de ajustes, o modelo representou um comportamento satisfat?rio em rela??o ao mecanismo proposto
92

Synthesis and characterization of catalysts used for the catalytic oxidation of sulfur-containing volatile organic compounds:focus on sulfur-induced deactivation

Darif, B. (Bouchra) 02 December 2016 (has links)
Abstract The work in this thesis concentrates on finding more active and durable catalysts for the demanding environmental application of the oxidation of sulfur-containing volatile organic compounds (S-VOCs). This application is challenging due to the high purification levels required and the catalyst deactivating nature of sulfur. In this thesis, dimethyldisulfide (DMDS) was used as the model molecule to represent S-VOCs since it is often present in odorous emissions and it is more difficult to treat than most of the other S-VOCs. It was found that the addition of a very small amount of Pt (0.3%) especially improves the selectivity of copper oxide based catalysts towards complete oxidation products ((carbon dioixide (CO2), water (H2O) and sulfur dioxide (SO2)) in DMDS oxidation. Catalyst characterization by transmission electron microscopy, temperature programmed reduction and X-ray photoelectron spectroscopy analyses suggests that this promoting effect is most likely due to the close interaction between Cu and Pt species on the bimetallic PtCu/γ-Al2O3 catalyst. The drawback of using the Al2O3 support is that it is not resistant towards sulfur poisoning. The deactivation of the self-made catalysts was studied with the help of an accelerated ageing procedure that was developed based on the information from the industrially aged volatile organic compound (VOC) catalysts. Industrial deactivation was caused by the sintering of the support and active metals and by the formation of metal sulfates with the support. After accelerated ageing, the silica doped alumina (Al2O3)0.8(SiO2)0.2 supported catalyst, showed remarkably promising results in terms of stability towards sulfur poisoning and the activity in DMDS oxidation was very close to that of the most active PtCu/Al2O3. The addition of less than 20% of SiO2 on the Al2O3 support led to a catalyst that is more selective and resistant to sulfur poisoning. / Tiivistelmä Väitöskirjassa tuotetaan uutta tietoa rikkipitoisten orgaanisten yhdisteiden (S-VOC) hapetukseen soveltuvien uusien katalyyttisten materiaalien synteesistä ja karakterisoinnista. S-VOC-yhdisteiden käsittely on vaativa katalyyttisen polton sovellus, koska näiden päästöjen käsittely edellyttää korkeaa puhdistustehoa, ja lisäksi yhdisteiden sisältämä rikki on katalyyttimyrkky. Tässä väitöskirjassa valittiin S-VOC-yhdisteitä edustavaksi malliaineeksi dimetyylisulfidi (DMDS), koska se on usein mukana käsiteltävissä S-VOC-päästöissä ja sen käsittely on vaativampaa kuin useiden muiden S-VOC-yhdisteiden käsittely. Tutkimustulosten mukaan hyvin pieni Pt-lisäys (0.3 %) parantaa erityisesti kuparioksidikatalyyttien selektiivisyyttä DMDS:n kokonaishapetustuotteiksi (CO2, H2O, SO2). Katalyyttien karakterisoinnin (läpäisyelektronimikroskopia, lämpötilaohjattu pelkistysreaktio, röntgensädefotoelektronispektroskopia) perusteella voidaan esittää parannuksen syyksi kuparin ja platinan läheinen kontakti bimetallisen PtCu/γ-Al2O3-katalyytin pinnalla. Al2O3-tukiaineen heikkoutena on sen deaktivoitumisherkkyys rikkiyhdisteiden läsnä ollessa. Väitöskirjatyössä valmistettujen katalyyttien deaktivitumista tutkittiin laboratoriomittakaavassa nopeutettujen ikäytyskokeiden avulla, jotka kehitettiin teollisessa käytössä deaktivoituneen katalyytin karakterisointien avulla saadun tiedon perusteella. Teollisessa käytössä olleen katalyytin deaktivoitumisen syyksi havaittiin tukiaineen ja aktiivisten metallien sintrautuminen sekä metallisulfidien muodostuminen tukiaineen kanssa. Nopeutettujen ikäytyskokeiden tulosten perusteella havaittiin, että piidioksidin lisäys alumiinioksiditukiaineeseen paransi tukiaineen rikin kestoa merkittävästi. Tutkimuksissa havaittiin myös, että piidioksidilla muokatun katalyytin aktiivisuus oli hyvin lähellä vastaavaa PtCu/γ-Al2O3-katalyytin aktiivisuutta. DMDS:n hapetuksessa selektiivisempi ja stabiilimpi katalyytti voidaan aikaansaada alle 20 %:n SiO2-lisäyksellä Al2O3-tukiaineeseen.
93

Synthèses, caractérisations et performances catalytiques des zéolithes nanoéponge de type structurale *BEA / Synthesis, characterization and catalytic performance of *BEA-type zeolites nanosponge

Astafan, Amir 30 May 2016 (has links)
La méthode à privilégier pour améliorer dans les zéolithes la diffusion des réactifs, des intermédiaires réactionnels et des produits est de raccourcir la longueur du chemin diffusionnel, c'est-à-dire de diminuer la taille des cristaux. La croissance des cristallites est fonction de la composition du gel de synthèse, du temps de cristallisation, de la température, etc. La maîtrise de cette croissance permet d'obtenir un large éventail de taille pouvant aller de plusieurs micromètres à seulement quelques dizaines de nanomètres. Dorénavant, il est possible de limiter le chemin diffusionnel à seulement 3 mailles élémentaires en inhibant lors de la synthèse hydrothermale la croissance des cristaux dans une direction privilégiée. Pour cela l'utilisation d'agent structurant organique très particulier de type géminé s'avère indispensable et donne dans le cas de la zéolithe de type *BEA un matériau hiérarchisé avec des cristaux zéolithiques de 4 nm d'épaisseur séparés par des mésopores structurés et réguliers. La morphologie de ce matériau ressemble à une éponge de mer.<br>Deux réactions modèles, hydroisomérisation du n-héxadécane et transformation de l'éthanol en hydrocarbures, démontrent que la diffusion des réactifs et des produits sont optimisées dans les nanoéponges de bêta. La stabilité et la sélectivité du catalyseur se trouvent alors améliorées au détriment, étonnamment, de l'activité. Cela vient du fait que l'extrême diminution de l'épaisseur des cristallites conduit à une augmentation du nombre d'aluminium en bouche de pores qui sont, bien que très accessibles, incapables de catalyser les réactions d'isomérisation et de craquage. Les aluminium proche de la surface externe, contrairement à ceux situés au cœur du cristal ne bénéficient pas des effets longues distances ce qui les rend moins forts. / The method to ameliorate the diffusion of reactants, reaction intermediates, and products inside the zeolite is by shortening the diffusion path length, i.e., crystals size. The growth of the crystals is a function of gel composition synthesis, crystallization time, temperature, etc. The mastering of this growth allows to obtain a wide range of the size which ranges from several micrometers to a few tens of nanometers. It is possible now to limit the diffusion path to only three unit cells by inhibiting the crystals' growth in one direction during the hydrothermal synthesis. For that, the use of a peculiar organic surfactant geminate is indispensable, it gives a hierarchical material with zeolitic crystals of 4 nm thickness separated by structured and regular mesopores in the case of *BEA type zeolite. The morphology of this material resembles a sea sponge.<br>Two reaction models, n-hexadecane hydroisomerization and ethanol transformation to hydrocarbons, demonstrate that the reactants and the products diffusion was optimized in the beta nanosponges. Surprisingly the catalyst stability and selectivity were improved instead of activity. In fact this is due to the extreme reducing of the zeolite crystals’ thickness that leads to increase the aluminum number in the pore mouth, which although very accessible, but incapable to catalyze the isomerization and cracking reactions. The aluminums near the external surface, in contrary to those in the crystal heart, do not benefit from the long distance effects, which makes them weaker.
94

Deactivation of oxidation catalysts by sulphur and phosphorus in diesel and gas driven vehicles

Kärkkäinen, M.-L. (Marja-Liisa) 28 November 2017 (has links)
Abstract The combustion of fuels in motor vehicles is one of the most significant causes of air emissions. The use of oxidation catalysts in exhaust gas emission treatment can reduce hydrocarbons (HCs) and carbon monoxide (CO) emissions by more than 90%. Fuels and engine lubricants contain impurities like sulphur (S) and phosphorus (P), which can have a significant effect on the activity and durability of oxidation catalysts. This thesis aims at increasing the current knowledge of the deactivation phenomena caused by sulphur and phosphorus in diesel and natural/bio gas oxidation catalysts. Accelerated laboratory scale sulphur, phosphorus and thermal treatments in gas-phase conditions were carried out for alumina (Al2O3) based platinum (Pt) and platinum-palladium (PtPd) metallic monolith diesel and natural gas oxidation catalysts. In addition, a vehicle-aged natural gas oxidation catalyst and an engine-bench-aged diesel oxidation catalyst were studied and used as a reference for the laboratory-scale-aged catalysts. BET-BJH, FESEM, TEM, XPS and DRIFT were used as characterization techniques to determine changes on the catalysts. The effect of accelerated deactivation treatments on the catalyst activity was determined using laboratory scale measurements in CO, HC and nitric oxide (NO) oxidation. Sulphur and phosphorus were found to cause morphological and chemical changes on the studied catalysts. Sulphur was found to be adsorbed vertically throughout the entire catalyst support from the catalyst surface to the metallic monolith, while phosphorus accumulated on the surface region of the precious metal containing catalysts. Both, sulphur and phosphorus, slightly increased the average size of the precious metal particles size and are adsorbed onto the alumina by chemical bonds. In addition, a partial transformation from PdO to Pd and a change in the shape of the precious metal particles due to phosphorus were detected. Due to the detected structural and chemical changes on the catalysts, sulphur and phosphorus treatments reduced the catalytic activity of the studied diesel and natural-gas-oxidation catalysts. Correspondence between real and simulated ageing was found and thus the used accelerated laboratory scale aging method can be stated to be a good tool to simulate sulphur and phosphorus exposure. / Tiivistelmä Moottoriajoneuvot ovat merkittäviä ilmapäästöjen aiheuttajia. Hapetuskatalyyttejä käyttämällä hiilimonoksidi- ja hiilivetypäästöistä pystytään poistamaan yli 90 %. Polttoaineet ja voiteluaineet sisältävät epäpuhtauksia kuten rikkiä ja fosforia, jotka voivat merkittävästi heikentää hapetuskatalyyttien aktiivisuutta ja kestävyyttä. Väitöskirjan tavoitteena on tuottaa uutta tietoa rikin ja fosforin aiheuttamasta diesel- ja maakaasukatalyyttien deaktivoitumisesta. Metalliseen monoliittiin tuettuja alumiinioksidipohjaisia platina- ja palladiumkatalyytteja ikäytetiin tekemällä niille rikki-, fosfori- ja lämpökäsittelyjä. Maantieikäytettyä maakaasuhapetuskatalyyttiä ja moottoripenkki-ikäytettyä dieselhapetuskatalyyttiä käytettiin laboratorioikäytettyjen katalyyttien referensseinä. Ikäytyskäsittelyjen aiheuttamat muutokset analysoitiin BET-BJH-, FESEM-, TEM-, XPS- ja DRIFT-menetelmillä. Käsittelyjen vaikutus katalyyttien hiilimonoksidin, hiilivetyjen ja typenoksidien hapetusaktiivisuuteen tutkittiin laboratoriomittakaavan aktiivisuuslaitteella. Rikki ja fosfori aiheuttivat rakenteellisia ja kemiallisia muutoksia tutkittuihin katalyytteihin. Rikki adsorboitui koko tukiaineeseen (tukiaineen pinnalta pohjalle), kun taas fosfori adsorboitui vain pinnan alueelle. Sekä rikki että fosfori kasvattivat jalometallipartikkeleiden kokoa sekä muodostivat alumiinioksidin kanssa yhdisteitä. Lisäksi fosforikäsittelyjen havaittiin osittain pelkistävän PdO:n Pd:ksi ja muuttavan jalometallipartikkelien muotoa. Havaitut rikin ja fosforin aiheuttamat rakenteelliset sekä kemialliset muutokset laskivat diesel- ja maakaasukatalyyttien hapetusaktiivisuutta. Laboratorioikäytyksillä havaittiin olevan hyvä korrelaatio todellisissa olosuhteissa tehtyjen ikäytysten kanssa ja tästä syystä työssä käytetyn laboratoriomittakaavan ikäytysmenetelmän voidaan todeta olevan hyvä työkalu simuloimaan rikin ja fosforin aiheuttamaa deaktivoitumista.
95

Hydrogen production from steam reforming of ethanol over an Ir/ceria-based catalyst : catalyst ageing analysis and performance improvement upon ceria doping / Production d'hydrogène par vapo-reformage de l'éthanol sur catalyseurs à base d'iridium sur cérine : analyse du vieillissement et optimisation des performances par dopage de la cérine

Wang, Fagen 23 October 2012 (has links)
Ce travail rapporte l’étude des processus de désactivation et des modifications d’un catalyseur Ir supportésur cérine en vaporeformage de l’éthanol. Différentes causes de désactivation ont été identifiées selon lesconditions opératoires : température, temps de contact et temps de réaction. La désactivation initiale,rapide mais limitée a été attribuée à la restructuration de surface de la cérine et à la formation d’unemonocouche d’intermédiaires de type acetate, carbonate et hydroxyls. En parallèle, une désactivationlente et progressive a été mise en évidence, ayant pour origine les changements structurels de l’interfaceentre la cérine et l’iridium, liés au frittage des particules d’iridium et à la restructuration profonde de lacérine. Par contre, la formation continue, à température modérée, d’une couche de carbone encapsulantissu de la polymérisation d’intermédiaires C2 n’a pas semblé contribuer significativement à ladésactivation du catalyseur dans nos conditions opératoires. Pour limiter ce phénomène de désactivation,des modifications ont été apportées au catalyseur. Le dopage du catalyseur par PrOx a permis defortement améliorer la capacité de stockage de l’oxygène et la stabilité thermique du catalyseur,entraînant une augmentation de son activité et de sa stabilité en vaporeformage de l’éthanol. Lecatalyseur Ir/CeO2 a ensuite subi une mise en forme de la cérine (nano-tubes), avec une influencesignificative sur l'activité et la stabilité en vaporeformage de l’éthanol, liée à des effets structuraux. Unemodélisation simplifiée de ces divers phénomènes a également contribué à soutenir les propositionsoriginales de ce travail. / The objective of the thesis was to analyze the ageing processes and the modifications of an Ir/CeO2catalyst for steam reforming of ethanol. Over a model Ir/CeO2 catalyst, the initial and fast deactivationwas ascribed to ceria surface restructuring and the build-up of intermediates monolayer (acetate,carbonate and hydroxyl groups). In parallel, a progressive and slow deactivation was found to come fromthe structural changes at the ceria/Ir interface linked to Ir sintering and ceria restructuring. Theencapsulating carbon, coming from C2 intermediates polymerization, did not seem too detrimental to theactivity in the investigated operating conditions. By doping ceria with PrOx, the oxygen storage capacityand thermal stability were greatly promoted, resulting in the enhanced activity and stability. The Ir/CeO2catalyst was then modified by changing the shape of ceria. It was found that the shape and therefore thestructure of ceria influenced the activity and stability significantly. A simplified modeling of theseprocesses has contributed to support the new proposals of this work.
96

Opportunities to Improve Aftertreatment Thermal Management and Simplify the Air Handling Architectures of Highly Efficient Diesel Engines Incorporating Valvetrain Flexibility

Mrunal C Joshi (8231772) 06 January 2020 (has links)
In an effort to reduce harmful pollutants emitted by medium and heavy duty diesel engines, stringent emission regulations have been imposed by the Environmental Protection Agency (EPA) and the California Air Resources Board (CARB). Effective aftertreatment thermal management is critical for controlling tail pipe outlevels of NOx and soot, while improved fuel efficiency is also necessary to meet greenhouse gas emissions standards and customer expectations. Engine manufacturers have developed and implemented several engine and non-engine based techniques for emission reduction, a few examples being: exhaust gas recirculation (EGR), use of delayed in-cylinder injections, exhaust throttling, electric heaters and hydrocarbon dosers. This work elaborates the use of variable valve actuation strategies for improved aftertreatment system (ATS) thermal management of a modern medium-duty diesel engine while presenting opportunities for simplification of engine air handling architecture.<div><br></div><div>Experimental results at curb idle demonstrate that exhaust valve profile modulation enables effective ATS warm-up without requiring exhaust manifold pressure (EMP) control. Early exhaust valve opening with internal exhaust gas recirculation (EEVO+iEGR) resulted in 8% lower fuel consumption and reduction in engine out emissions. Late exhaust valve opening with internal EGR in the absence of EMP control was able to reach exhaust temperature of 287<sup>◦</sup>C, without a penalty in fuel consumption or emissions compared to conventional thermal management. LEVO combined with EMP control could reach turbine outlet temperature of nearly 460<sup>◦</sup>C at curb idle.<br></div><div><br></div><div>LEVO was studied at higher speeds and loads to assess thermal management benefits of LEVO in the absence of EMP control, with an observation that LEVO can maintain desirable thermal management performance up to certain speed/load conditions, and reduction in exhaust flow rate is observed at higher loads due to the inability of LEVO to compensate for loss of boost associated with absence of EMP control.<br></div><div><br></div><div>Cylinder deactivation (CDA) combined with additional valvetrain flexibility results in low emission, fuel-efficient solutions to maintain temperatures of a warmed-up ATS. Late intake valve closing, internal EGR and early exhaust valve opening were studied with both three cylinder and two cylinder operation. Some of these strategies showed additional benefits such as ability to use earlier injections, elimination of external EGR and operation in the absence of exhaust manifold pressure control. Three cylinder operation with LIVC and iEGR is capable of reaching exhaust temperatures in excess of 230<sup>◦</sup>C with atleast 9% lower fuel consumption than three cylinder operation without VVA. Three cylinder operation with early exhaust valve opening resulted in exhaust temperature of nearly 340<sup>◦</sup>C, suitable for extended idling operation. Two cylinder operation with and without the use of valve train flexibility also resulted in turbine outlet temperature relevant for extended idling (and low load operation), while reducing fuel consumption by 40% compared to the conventional thermal management strategy.<br></div><div><br></div><div>A study comparing the relative merits of internal EGR via reinduction and negative valve overlap (NVO) is presented in order to assess trade-offs between fuel efficient stay-warm operation and engine out emissions. This study develops an understanding of the optimal valve profiles for achieving reinduction/NVO and presents VVA strategies that are not cylinder deactivation based for fuel efficient stay-warm operation. Internal EGR via reinduction is demonstrated to be a more fuel efficient strategy for ATS stay-warm. An analysis of in-cylinder content shows that NOx emissions are more strongly affected by in-cylinder O2 content than by method of internal EGR.<br></div>
97

Design and Utilization of New Organotellurium Chain Transfer Agents for Advanced Polymer Synthesis / 先進高分子合成のための新規有機テルル連鎖移動剤の設計と利用

Fan, Weijia 23 May 2019 (has links)
京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21963号 / 工博第4618号 / 新制||工||1720(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 山子 茂, 教授 辻井 敬亘, 教授 大内 誠 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM
98

Čtyřválcový vznětový motor s vypínáním válců / Four-cylinder diesel engine with cylinder deactivation

Weidner, Lukáš January 2017 (has links)
The aim of this thesis is design crankshaft for four-cylinder diesel engine with cylinder deactivation. Further, to perform stress analysis of designed crankshaft with considering torsional vibration.
99

Čtyřválcový zážehový motor s vypínáním válců / Four-cylinder gasoline engine with cylinder deactivation

Steigl, Vladimír January 2017 (has links)
The aim of this diploma thesis is design of configuration and balancing of crankshaft which is determined for four-cylinder gasoline engine. The thesis investigates kinematics, dynamics and possible ways of balancing the inertial forces and moments of the rotating and sliding parts of the central crank mechanism. Subsequently, the 3D CAD model is designed according to the presented drawing. It is transformed into a spare torsion system, from which the calculations of its own and forced torsional vibrations are based. The proposed 3D CAD model is then spatially transmitted in the FEA software Ansys Workbench and modified (boundary conditions, etc.) in the FEA software Ansys Mechanical APDL so that it can be calculated according to the selected LSA method. From the selected results of the LSA method, the crankshaft safety factor against fatigue damage is calculated.
100

Prospective Memory and Intention Deactivation: Challenges, Mechanisms and Modulators

Möschl, Marcus 20 December 2019 (has links)
From the simple act of picking up a glass of water while talking to someone at a party, to remembering to swing by the bike shop to pick up an inner tube while riding through traffic on our way home from the office, intentions guide and alter our behavior—often while we are busily engaged in other ongoing tasks. Particularly, performing delayed intentions, like stopping at the bike shop on our way home, relies on a set of cognitive processes summarized as prospective memory (PM) that enable us to postpone intended actions until a later point in time (time-based PM) or until specific reminders or PM cues signal the appropriate opportunity to retrieve and perform an intended action (event-based PM). Interestingly, over the past decades a growing number of studies showed that successfully completing an event-based intention does not necessarily lead to its immediate deactivation. Instead, no-longer-relevant PM cues can incur so-called aftereffects that impair task performance and sometimes even trigger erroneous repetitions of the intended action (i.e., commission errors). Although in our everyday lifes we frequently rely on both PM and intention deactivation, still relatively little is known about how our cognitive system actually manages to deactivate completed intentions, under which conditions this may fail, and how well PM and intention deactivation function under extreme conditions, like acute stress. In order to answer these questions, I first conducted a comprehensive review of the published literature on aftereffects of completed intentions. Here, I found that although intentions can incur aftereffects in terms of commission errors and performance costs that most likely result from continued intention retrieval, they generally seem to be deactivated or even inhibited at some point. Most importantly, this deactivation process does not operate like a light switch but dynamically moves along a continuum from complete reactivation to complete deactivation of intentions, and is substantially modulated by factors that also affect retrieval of intentions prior to their completion. Specifically, intention deactivation is most likely to fail when we remain within the same context in which we originally completed the intention and encounter no-longer-relevant PM cues that are extremely salient and were strongly linked to the intended action. Subsequently, in Study 1 I directly tested a dual-mechanisms account of aftereffects of completed intentions. Building on findings of impaired intention deactivation in older adults who often show deficits in cognitive-control abilities, this account posits that aftereffects and commission errors in particular stem from a failure to exert cognitive control when no-longer-relevant PM cues trigger retrieval of an intention. Accordingly, intention deactivation should hinge on the availability of cognitive-control resources at the moment we encounter no-longer-relevant PM cues. In order to test this, I assessed aftereffects of completed intentions in younger and older adults while manipulating transient demands on information processing during encounters of no-longer-relevant PM cues on a trial-by-trial basis. In Experiment 1, nominally more older adults than younger adults made a commission error. Additionally, medium demands on cognitive control substantially reduced aftereffects compared to low and high demands (i.e., u-shaped relation). In Experiment 2, which extended this manipulation but only tested younger adults, however, this control-demand effect did not replicate. Instead, aftereffects occurred regardless of cognitive-control demands. The lack of a consistent control-demand effect on aftereffects across two experiments, suggested that cognitive control either only plays a minor role for the occurrence of aftereffects or that, more likely, intention deactivation hinges on other specific cognitive-control abilities, like response inhibition. In two subsequent studies, I extended this research and tested the effects of acute stress—a potent modulator of cognitive-control functioning—on PM and intention deactivation. Previous studies showed that, under moderate demands, acute stress had no effect on PM-cue detection, intention deactivation or performance costs that presumably arise from monitoring for PM cues. Importantly, however, based on these studies it remained unclear if acute stress affects PM and intention deactivation under high demands, as has been observed, for instance, with working-memory performance. To test such a potential demand-dependence of acute stress effects on PM, I first assessed the effects of psychosocial stress induction with the Trier Social Stress Test on PM and intention deactivation when detecting PM cues and intention deactivation were either low or high demanding (Study 2). Building on this work, I then tested the effects of combined physiological and psychosocial stress induction with the Maastricht Acute Stress Test on PM and the ability to track one’s own performance (i.e., output monitoring), when PM-cue detection was difficult and ongoing tasks additionally posed either low or high demands on working memory (Study 3). Despite successful stress induction (e.g., increased levels of salivary cortisol and impaired subjective mood), both studies showed that PM-cue detection and intention retrieval were not affected by acute stress under any of these conditions. Study 2 revealed a tendency for a higher risk of making commission errors under stress when no-longer-relevant PM cues were salient and difficult to ignore. Study 3 additionally showed that acute stress had no effect on output monitoring. Most importantly, however, across the different PM tasks and stress-induction protocols in these studies, acute stress substantially reduced performance costs from monitoring for PM cues, but did so only when PM-cue detection was difficult. This effect suggested that, depending on task demands, acute stress might shift retrieval processes in PM away from costly monitoring-based retrieval towards a more economic spontaneous retrieval of intended actions. In summary, the present thesis suggests that the processes underlying prospective remembering and intention deactivation are tightly woven together and are only selectively affected by cognitive-control availability and effects of acute stress. With this, it contributed substantially to our understanding of these essential cognitive capacities and their reliability. My research showed that PM is remarkably resilient against effects of acute stress experiences when remembering intended actions is supported by external reminders. Acute stress may actually make monitoring for such reminders more efficient when they are hard to detect. Additionally, it showed that, in most circumstances, we seem to be able to successfully and quickly deactivate intentions once they are completed. It is only under some conditions that intention deactivation may be slow, sporadic or fail, which can lead to continued retrieval of completed intentions. While this seems not to be affected by transient demands on information processing during encounters of no-longer-relevant PM cues, intention deactivation might become difficult for older adults and stressed individuals when no-longer-relevant reminders of intentions easily trigger the associated action and are hard to ignore.

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