Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / As propriedades fÃsico-quÃmicas do Ãster EtÃlico do Ãleo de Mamona (EEOM) foram estimadas a partir de modelos teÃricos e anÃlises experimentais. Por nÃo ser um combustÃvel comercial, o EEOM foi manufaturado por meio de um processo de fabricaÃÃo denominado (Transesterification Double Step Process) TDPS. AtravÃs do mÃtodo de contribuiÃÃo de grupos, as propriedades crÃticas e o ponto de ebuliÃÃo normal foram estimados. Utilizando os valores das propriedades crÃticas e correlaÃÃes matemÃticas, estimaram-se a tensÃo superficial, a entalpia de vaporizaÃÃo, a pressÃo de vapor, a condutividade tÃrmica, a viscosidade e a densidade. A anÃlise experimental do EEOM foi conduzida utilizando tÃcnicas tradicionalmente associadas à pesquisa de densidade e viscosidade de combustÃveis. Na anÃlise experimental de viscosidade utilizou-se um viscosÃmetro copo Ford. TambÃm foram analisadas experimentalmente as misturas ternÃrias do EEOM, etanol e diesel comercial em diversas fraÃÃes volumÃtricas. A anÃlise das misturas ternÃrias vem como uma alternativa para amenizar os valores de viscosidade e densidade do EEOM no combustÃvel de uso final, estimando os valores de fraÃÃes volumÃtricas que podem atender as normas brasileiras e europeias. Os resultados das propriedades fÃsico-quÃmicas servirÃo como base para rotinas computacionais de simulaÃÃo aplicadas ao estudo de emissÃes de poluentes e formaÃÃo do jato combustÃvel para o EEOM. / The physicochemical properties of the Ethyl Ester of Castor Oil (EECO) were estimated from theoretical models and experimental analysis. As it is not a comercial fuel, the EECO has been manufactured by a special fabrication process denominated (Transesterification Double Step Process) TDPS. Through the group contribution method, critical properties and normal boiling point were estimated. Using the values of the critical properties and mathematical correlations, were surface tension, enthalpy vaporization, vapor pressure, thermal conductivity, viscosity and density estimated. The experimental analysis of EEOM was conducted using techniques traditionally associated with research of density and viscosity of fuel. In the experimental analysis of viscosity it was used a Ford cup viscometer. As an alternative to alleviate the values of viscosity and density of the fuel EECO in ultimate use, as well as analyzed mixtures EECO, ethanol and diesel trade in various volume fractions, estimating the values that can meet the Brazilian and European standards. The results of the physical and chemical properties will serve as a basis for computer simulation routines applied to the study of emissions and formation of jet fuel for EECO.

[pt] Há algum tempo biocombustíveis renováveis são potenciais soluções sugeridas às questões de emissão de poluentes e dependência da sociedade aos derivados fósseis. Biodiesel e etanol são combustíveis comerciais renováveis candidatos à substituição das fontes fósseis, especialmente, em motores de ignição por compressão, os quais são tipicamente mais eficientes do que aqueles de ignição por centelha. Misturas ternárias de diesel, biodiesel e etanol formam estratégias de substituição parcial do diesel aplicáveis em motores de ignição por compressão sem a necessidade de grandes adaptações. Nesta dissertação realizaram-se avaliações experimentais em um motor multi-cilíndrico de ignição por compressão (MWM 4.10 TCA), abastecido com misturas de diesel, biodiesel (até 15 por cento em teor volumétrico) e etanol anidro (até 20 por cento em teor volumétrico). Cada mistura ternária é composta por diferentes proporções do álcool e sempre com a concentração volumétrica de 1 por cento de um aditivo estabilizador da mistura. Portanto, os testes associam substituições parciais do diesel por biocombustíveis a avaliações de desempenho do motor e da combustão das misturas, sob algumas condições de carga, regimes de rotação e instantes de injeção de combustível. Os testes realizados indicam que misturas com 20 por cento em volume de concentração de etanol experimentam inícios de combustão até 4,7 graus CA mais atrasados. Porém, a busca de instantes otimizados na injeção de combustível trouxe melhorias ao desempenho do motor, permitiu conversões energéticas mais vantajosas do etanol na ignição por compressão frente à ignição por centelha, além de minimizar efeitos do etanol em retardar o início da combustão. / [en] Renewable biofuels have been proposed for a long time as an alternative to the issues concerned to pollutants emission and also society s liability to fossil fuels. Biodiesel and ethanol are renewable commercial fuel candidates for fossil fuels substitution, especially, in compression ignition engines, which are typically more efficient than the spark ignition ones. Diesel s partial replacement, such as the substitution by ternary blends formed by diesel, biodiesel and ethanol, is a strategy applicable to compression ignition engines without the need of further modifications. In this dissertation tests were run in a multi-cylinder compression ignition engine (MWM 4.10 TCA), fueled with diesel, biodiesel (up to 15 percent in volumetric content) and anhydrous ethanol (up to 20 percent in volumetric content) blends. Each mixture should be composed by different alcohol s proportions and always containing a 1 percent volumetric concentration of additive in order to ensure ternary s blend stability. Therefore, tests try to ally diesel s partial replacement by biofuels with engine performance and blends combustion assessment, under some combinations of load, engine speed and injection timing conditions. The tests performed indicate that the start of the combustion experienced up to 4.7 degrees CA postponements, when fueled with a 20 percent ethanol volumetric concentration blend. Still, optimized injection timing investigation brought improvements to engine performance, allowed better ethanol energetic conversions through compression ignition when compared to spark ignition and could also minimize delays caused by ethanol s presence in the beginning of the combustion.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18593号 / 工博第3954号 / 新制||工||1608(附属図書館) / 31493 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 伊藤 紳三郎, 教授 木村 俊作, 教授 辻井 敬亘 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Ce travail vise à obtenir une morphologie cœur-peau directement lors du mélangeage à l’état fondu de polymères ternaires PLA/PBAT/PA. Le but final est d'améliorer la ténacité de l'acide polylactique (PLA). La morphologie des mélanges de polymères multi-phases est contrôlée par la thermodynamique du système. La morphologie des mélanges ternaires peut être prédite à partir des valeurs relatives des trois coefficients d'étalement caractérisant le triplet de polymères. Les coefficients d'étalement sont calculés à partir des valeurs des tensions interfaciales entre les composants binaires. La détermination des tensions interfaciales entre PLA, poly (butylène adipate-co-téréphtalate) (PBAT) et un copolyamide (PA) prédit une morphologie dispersée complexe dans la matrice PLA où les sous-inclusions PA sont partiellement encapsulées dans la phase PBAT. Cette morphologie a été obtenue par mélange à l'état fondu des trois composants, comme observé par les observations en microscopie électronique à balayage. Dans une seconde étape, une compatibilisation sélective a été utilisée pour modifier l'emplacement des sous-inclusions de PA. A cette fin, deux copolymères diblocs PBAT-b-PLA, PA-b-PBAT ont été synthétisés. La présence des copolymères diblocs nous permet de modifier la tension interfaciale des couples PLA/PBAT, PA/PBAT. Cette modification de l'équilibre de tension interfaciale modifie avec succès la morphologie, passant d’une semi-encapsulation à une encapsulation complète des sous-inclusions de PA dans les gouttes de PBAT. La performance mécanique de ce mélange ternaire a été évaluée. / This work aims at achieving direct core-shell morphologies in ternary PLA/PBAT/PA polymer blends by melt mixing. The final goal is to improve the toughness of polylactic acid (PLA). The morphology of multi-phase polymer blends is controlled by the thermodynamics of the system. The morphology of ternary blends can be predicted from the relative values of the three spreading coefficients characterizing the triplet of polymers. Spreading coefficients are calculated from the values of interfacial tensions between binary components. The determination of interfacial tensions between a PLA, a poly(butylene adipate-co-terephthalate) (PBAT) and a copolyamide (PA) predicts a complex dispersed morphology in the PLA matrix where PA subinclusions are partly encapsulated in the PBAT phase. This morphology was obtained by melt mixing the three components, as observed by scanning electron microscopy. In a second step, selective compatibilization was used to modify the PA sub-inclusion location. To this end, PBAT-b-PLA and PA-b-PBAT di-block copolymers were synthesized. The presence of the di-block copolymers enabled to modify the interfacial tension in PLA/PBAT and PA/PBAT. The modification of the interfacial tension balance was shown to successfully change the morphology from semi-encapsulation to full encapsulation of PA sub-inclusions in the PBAT drops. The mechanical performance of this ternary blend was evaluated.

L’objectif final de la thèse est l'impression de la couche photo-active ternaire d'une cellule solaire organique en utilisant deux approches: l'une concerne l'apport de nanotubes de carbone (SWCNT) pour améliorer les propriétés de transport, l'autre concerne la préparation de mélanges ternaires de matériaux pour contrôler la couleur des cellules. Les encres pour la couche active incluant des SWCNT fonctionnalisés sont composées d’un donneur d'électron (polymère) (poly(3-hexylthiophène), [P3HT]) et d’un accepteur d'électron ( [6,6]-phényl C61-butyrique ester méthylique d'acide [PCBM]) et ont été développées pour la fabrication de cellules inversées. Ces cellules sont réalisées sur substrats de verre pour l'optimisation de leurs performances, puis sur substrats plastiques pour les applications. Diverses couches d'interfaces ont été testées, qui incluent l'oxyde de zinc (ZnO, couches obtenues par pulvérisation ionique (IBS) ou à partir de solutions de nanoparticules) pour la couche de transport d'électrons et le PEDOT:PSS, le P3MEET, le V2O5 et le MoO3 pour la couche de transport de trous. Des essais ont été effectués avec et sans CNT afin d’étudier leur impact sur les performances. Des résultats similaires sont obtenus dans les deux cas. Il était attendu que les CNT améliorent les performances, ce qui n’a pas été observé pour le moment. Des travaux supplémentaires sont donc nécessaires au niveau de la formulation de la couche active.Avec trois polymères de couleur rouge (P3HT), bleu (B1) et vert (G1), nous avons préparé des mélanges ternaires efficaces permettant l'obtention de couleurs jusque là indisponibles . Nous avons fait une étude sur le piégeage et les mécanismes de diodes parallèles associés aux mélanges. En général, nous avons constaté que les mélanges ternaires de polymères bleu et vert peuvent être décrits par une mécanisme de diodes parallèles, sans entrainer de perte de performances, ce qui n'est pas possible pour les systèmes P3HT:B1 :PCBM et P3HT:G1:PCBM qui se piègent mutuellement. L’objectif final du projet est l'impression de la couche photo-active ternaire d'une cellule solaire organique, composites ternaires (polymère:polymères:acceptor) ou dopés avec les SWCNT. Cette étape nécessite encore des développements futurs. / Two approaches were followed to achieve increased control over properties of the photo-active layer (PAL) in solution processed polymer solar cells. This was accomplished by either (1) the addition of functionalized single-walled carbon nanotubes (SWCNTs) to improve the charge transport properties of the device or (2) the realization of dual donor polymer ternary blends to achieve colour-tuned devices.In the first component of the study, P3HT:PC61BM blends were doped with SWCNTs with the ambition to improve the morphology and charge transport within the PAL. The SWCNTs were functionalized with alkyl chains to increase their dispersive properties in solution, increase their interaction with the P3HT polymer matrix, and to disrupt the metallic characteristic of the tubes, which ensures that the incorporated SWCNTs are primarily semi-conducting. P3HT:PCBM:CNT composite films were characterized and prepared for use as the photoactive layer within the inverted solar cell. The CNT doping acts to increase order within the active layer and improve the active layer’s charge transport properties (conductivity) as well as showed some promise to increase the stability of the device. The goal is that improved charge transport will allow high level PSC performance as the active layer thickness and area is increased, which is an important consideration for large-area inkjet printing. The use of ternary blends (two donor polymers with a fullerene acceptor) in bulk-heterojunction (BHJ) photovoltaic devices was investigated as a future means to colour-tune ink-jet printed PSCs. The study involved the blending of two of the three chosen donor polymers [red (P3HT), blue (B1), and green (G1)] with PC61BM. Through EQE measurements, it was shown that even devices with blends exhibiting poor efficiencies, caused by traps, both polymers contributed to the PV effect. However, traps were avoided to create a parallel-like BHJ when two polymers were chosen with suitable physical compatibility (harmonious solid state mixing), and appropriate HOMO-HOMO energy band alignment. The parallel diode model was used to describe the PV circuit of devices with the B1:G1:PC61BM ternary blend.

This paper discusses the potential of gasoline, ethanol and methanol ternary blend as an alternative passenger car fuel in Sweden. Sweden has set various targets aimed to reduce its GHG emissions and to increase the share of renewables in the transportation sector. Nevertheless, the majority of the energy consumed in the road transportation sector still comes from fossil fuels. In order to replace the energy supply of fossil fuels by more renewable fuels, the potential of alternative renewable fuels needs to be explored. Therefore, the potential of a domestically produced ternary blend of Gasoline‐Ethanol‐ Methanol (GEM) fuel blend is analysed in this report. In order to test whether it has the potential to become a successful alternative fuel, an analysis is performed on the: methanol and ethanol production potential from domestic second‐generation feedstocks, the selection of the most suitable production pathways of the biofuels, the potential for a Swedish GEM fuel distribution infrastructure, the economic competitiveness of GEM fuel, and lastly on the environmental impact of the shift from cars running on neat gasoline to GEM fuel. In order to perform the analysis, two scenarios are developed for projecting the share of the GEM cars(cars running on GEM fuel blends) in the Swedish passenger car fleet, considering a time horizon from 2017 to 2030. In Scenario 1, a high share of passenger cars running on GEM fuel is obtained with 22 percent by 2030. In Scenario 2, a low share of cars running on GEM fuel is obtained with 17 percent by 2030. In both scenarios, the passenger cars running on GEM fuel take over the share of cars running on gasoline. The scenarios serve to project the energy demand for GEM fuels. By 2030, the projected energy demand for GEM fuels is 9.7 and 7.5 TWh for Scenario 1 and Scenario 2, respectively. From the biofuel potential studies, it can be concluded that the production potential of the alcohol fuels, derived from currently untapped domestic secondary resources, exceeds the projected energy demand of 9.7 and 7.5 TWh in 2030. According to this thesis, the production potential of 2nd generation ethanol and methanol are 36 and 61.1 TWh, respectively, by 2030. Moreover, the study shows that the majority of the existing fuel distribution network of E85 and gasoline, which is forecasted to have a significant overcapacity in the same time‐span as the scenarios, can be utilized in a GEM fuel distribution network. As a consequence, no major investments are required to develop a Swedish GEM fuel distribution network. Regarding the selection of the biofuel production pathways, this study indicates the most suitable way of producing methanol is by black‐liquor gasification. Regarding second‐generation ethanol, this thesis indicates that the fermentation forestry residues is the most beneficial production pathway. The biofuel production pathways are selected based on the energy yield ratios, the biofuel production cost and biomass feedstock cost. Moreover, this study demonstrates that under the current Swedish policies, GEM fuels blends are economic competitive with gasoline and E85. In order to test the economic competitiveness, a pay‐off curve was developed based on the pump price of gasoline and fuel economy of GEM fuel blends. This study shows the pump prices of GEM fuel blends pay‐off in comparison to gasoline. This analysis indicates that the pump prices of GEM fuel blends lays between 0.87 and 0.92 euro per liter. Regarding the environmental impact, this study indicates that the amount of GHG emissions avoided varies between 10.1 and 13.3 million metric tons CO2eq in Scenario 1. In Scenario 2, the amount of GHG emissions that can be avoided varies between 8.6 and 11.3 million metric tons CO2eq. Moreover, this study indicates that high methanol containing GEM fuel blend are more favourable in terms of biomass utilization, and high ethanol containing GEM fuel blends are more favourable in terms of economy and GHG savings.