京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第20447号 / 農博第2232号 / 新制||農||1050(附属図書館) / 学位論文||H29||N5068(農学部図書室) / 京都大学大学院農学研究科農学専攻 / (主査)教授 北島 宣, 教授 田尾 龍太郎, 教授 土井 元章 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

Im Rahmen dieser Arbeit wird ein physikalisches Modell für weichelastische EVA-Schaumstoffe entwickelt, das das mechanische Verformungsverhalten (Spannungs-Verformungs-Kurve) bei der Interaktion zwischen Sportler und Sportgerät am Beispiel eines Laufschuhs anwendungsgerecht – d.h. bei hoher Verformung und Belastungsgeschwindigkeit – kennzeichnet. Im Stand der Technik werden als Einflussfaktoren auf das mechanische Verformungsverhalten von Weichschäumen die Parameter Schaumdichte, Zellgröße bzw. Zelldurchmesser, Schaumhärte und Verformungsgeschwindigkeit ermittelt. Diese werden für die vorliegenden vier Versuchsmaterialien analysiert, wobei die letzten zwei Parameter im Modell Berücksichtigung finden. Das Modell setzt sich aus einem Matrix- und einem Gasphasenanteil zusammen. Der Matrixphasenanteil wird experimentell bei der jeweiligen Verformungsgeschwindigkeit bestimmt, wohingegen der Gasphasenanteil der in den Zellen komprimierten Luft auf einem physikalischen Zusammenhang beruht und anhand der gemessenen Schaumhärte und des Atmosphärendrucks bei der jeweiligen Verformung berechnet wird. Die Voraussetzungen für die Verwendung des Modells, zu denen inkompressible Matrixphase, Geschlossenzelligkeit und keine Querausdehnung des Schaums zählen, werden vorab umfangreich geprüft. Zusammenfassend lässt sich aussagen, dass das gewählte Modell eine gute Übereinstimmung mit den experimentell bestimmten Ergebnissen erzielt. Dies wird anhand der Mittelwertes der Differenz von experimentell ermittelten zu modellierten Daten bestimmt, für den ein Wert von 7 % berechnet wird. / The purpose of this doctoral thesis is developing a physical model for flexible foam materials (e.g. ethylene/vinyl acetate foam) characterizing the mechanical deformation behavior (stress-strain-curve) at the interaction between athlete and sports equipment (e.g. running footwear) during high deformation and high loading rate. Previous studies described various parameters influencing the mechanical deformation behavior of flexible foams: foam density, cell size / cell diameter, foam hardness and loading rate. These parameters are being analyzed for the four present foams whereof the last two parameters were considered in the model. The model consists of a matrix phase measured experimentally at required loading rate multiplied with a correction factor and a gas phase of the air compressed in the foam cells which is calculated by atmospheric pressure and foam hardness. The requirements (incompressible matrix phase, closed cells and zero Poisson ratio) for using the model are verified first of all. In conclusion, the developed model presents a good accordance with the experimental data calculated by a mean difference between experimental and modeled data of 7 %.

A nêspera (Eriobotrya japonica Lindl.) é uma fruta do tipo pomo, que tem sido cultivada principalmente no estado de São Paulo. Cinco cultivares de nêspera foram selecionadas por se destacarem no sabor e na capacidade produtiva. Foi realizado o estudo das mudanças fisiológicas e físico-químicas dos frutos durante o desenvolvimento e o período pós-colheita. Amostras das cultivares (Centenária, Mizuho, Mizumo, Néctar de Cristal e Mizauto) foram colhidas semanalmente conforme o avanço do estádio de desenvolvimento (na planta), desde a fase verde dos frutos até se tornarem maduros. Os frutos maduros para estudo do período pós-colheita foram colhidos seguindo critérios adotados por produtores, através da cor dos frutos. As determinações físico-químicas realizadas nas nêsperas maduras foram umidade, fibra, ácido ascórbico, açúcares solúveis (glicose, frutose, sacarose e sorbitol), ácidos orgânicos e carotenóides. Durante o período de desenvolvimento das nêsperas, as curvas de respiração decresceram progressivamente, e houve um considerável aumento na produção de etileno, precedendo o aumento na concentração de açúcares e as mudanças de coloração dos frutos (verde a amarela ou alaranjada). A composição de açúcares e ácidos dos frutos maduros foi semelhante a encontrada nos frutos precocemente maduros durante o desenvolvimento na planta. Portanto, a observação visual da cor não foi apropriada para a definição do ponto ideal de colheita. Durante o período póscolheita, as curvas de respiração e de produção de etileno das cultivares tenderam a queda, mostrando comportamento típico de frutos não-climatéricos. O estudo fisiológico e físico-químico das cinco cultivares de nêspera permitiu conhecer melhor o padrão de amadurecimento de cada cultivar, e assim obter informações que auxiliem na definição do ponto ideal de colheita, e que permitam obter frutos de boa qualidade e apropriados para distribuição comercial. / Loquat (Eriobotrya japonica Lindl.) fruit is a pome fruit cultivated mainly in the state of São Paulo. Five loquat fruit cultivars were selected to analysis mainly by their high productivity and taste. Physiological and physico-chemical changes were analised during development and ripening fruit. Samples were harvest weekly according to progress in development stage (in the tree), since imature stage (green) until mature stage. Mature stage to harvest was defined by fruit color, like methods\' producer. The physico-chemical parameters analysed were moist value, fiber, ascorbic acid, soluble sugars (glucose, fructose, sucrose and sorbitol), organic acids and carotenoids. During development of loquat fruits, the respiration levels decreased, and show a increase in ethylene levels, which was associed with increase of sugar concentration in the pulp and the changes of fruit color (green to yellow or orange color). According to sugars and acids levels during development (in the tree) and in ripe stage, the composition in ripe fruits was similar to that early mature fruits analyzed during development in the tree. The visual determination of color was not appropriate to define the harvest point of fruits. During postharvest period of the cultivars, the levels in respiration and ethylene production decreased, which is a typical pattern of non-climacteric fruits. The study of physiological and physico-chemical characteristics of loquat cutivars contribute to know the ripening pattern of each cultivar and to auxiliary in the definition of best mature point to harvest and to comercial distribution.

Universiẗat, Diss., 2003--Kaiserslautern.

Universiẗat, Diss., 2004--Düsseldorf.

A nêspera (Eriobotrya japonica Lindl.) é uma fruta do tipo pomo, que tem sido cultivada principalmente no estado de São Paulo. Cinco cultivares de nêspera foram selecionadas por se destacarem no sabor e na capacidade produtiva. Foi realizado o estudo das mudanças fisiológicas e físico-químicas dos frutos durante o desenvolvimento e o período pós-colheita. Amostras das cultivares (Centenária, Mizuho, Mizumo, Néctar de Cristal e Mizauto) foram colhidas semanalmente conforme o avanço do estádio de desenvolvimento (na planta), desde a fase verde dos frutos até se tornarem maduros. Os frutos maduros para estudo do período pós-colheita foram colhidos seguindo critérios adotados por produtores, através da cor dos frutos. As determinações físico-químicas realizadas nas nêsperas maduras foram umidade, fibra, ácido ascórbico, açúcares solúveis (glicose, frutose, sacarose e sorbitol), ácidos orgânicos e carotenóides. Durante o período de desenvolvimento das nêsperas, as curvas de respiração decresceram progressivamente, e houve um considerável aumento na produção de etileno, precedendo o aumento na concentração de açúcares e as mudanças de coloração dos frutos (verde a amarela ou alaranjada). A composição de açúcares e ácidos dos frutos maduros foi semelhante a encontrada nos frutos precocemente maduros durante o desenvolvimento na planta. Portanto, a observação visual da cor não foi apropriada para a definição do ponto ideal de colheita. Durante o período póscolheita, as curvas de respiração e de produção de etileno das cultivares tenderam a queda, mostrando comportamento típico de frutos não-climatéricos. O estudo fisiológico e físico-químico das cinco cultivares de nêspera permitiu conhecer melhor o padrão de amadurecimento de cada cultivar, e assim obter informações que auxiliem na definição do ponto ideal de colheita, e que permitam obter frutos de boa qualidade e apropriados para distribuição comercial. / Loquat (Eriobotrya japonica Lindl.) fruit is a pome fruit cultivated mainly in the state of São Paulo. Five loquat fruit cultivars were selected to analysis mainly by their high productivity and taste. Physiological and physico-chemical changes were analised during development and ripening fruit. Samples were harvest weekly according to progress in development stage (in the tree), since imature stage (green) until mature stage. Mature stage to harvest was defined by fruit color, like methods\' producer. The physico-chemical parameters analysed were moist value, fiber, ascorbic acid, soluble sugars (glucose, fructose, sucrose and sorbitol), organic acids and carotenoids. During development of loquat fruits, the respiration levels decreased, and show a increase in ethylene levels, which was associed with increase of sugar concentration in the pulp and the changes of fruit color (green to yellow or orange color). According to sugars and acids levels during development (in the tree) and in ripe stage, the composition in ripe fruits was similar to that early mature fruits analyzed during development in the tree. The visual determination of color was not appropriate to define the harvest point of fruits. During postharvest period of the cultivars, the levels in respiration and ethylene production decreased, which is a typical pattern of non-climacteric fruits. The study of physiological and physico-chemical characteristics of loquat cutivars contribute to know the ripening pattern of each cultivar and to auxiliary in the definition of best mature point to harvest and to comercial distribution.

This thesis is focused on experiments, goal of which is to separate protective glass apart from thin layer solar panel. This could lead to less expensive and more efficient recycling. We try to achieve the separation of the glass by thawing ethylene vinyl acetate layer, which serves as insulant and bonding material. Experiments are concluded in high temperature dryer and high temperature vacuum oven on samples of thin layer solar panel, which is for the purposes of experiments cut into same pieces by water jet cutting machine. The initiatory experiments in dryer and oven are to determine value of ethylene vinyl acetate thaw point in tested samples of panel. The thaw point is determined to be 340 °C. When exposed to this temperature, the ethylene vinyl acetate thaws enough for glass to be able to be extracted with minimal physical strength. The process is accompanied by fire destruction of tedlar layer and creation of exhaust gases. Following experiments in vacuum and nitrogen environment are to test their influence on thawing process. Exposing sample to temperature of 340 °C in vacuum led to no new results. Exposing sample to temperature of 340 °C in nitrogen environment prevented fire and achieved same level of thawing of ethylene vinyl acetate while creating less exhaust gases. Even though the fire was prevented, tedlar layer was still destroyed by the high temperature. Furthermore, particles of evaporated ethylene vinyl acetate condensed on surface of module in form of dust. Following experiments studied absorption of panel and influence of accessible solvents on thawing process. It was determined that panel is able to absorb approximately 2 % of acetone, 0,4 % of isopropyl alcohol and 0,11 % of distilled water in its own weight. Experiments with modules soaked in these solvents proved no new results in thawing process. By observing samples of ethylene vinyl acetate taken from module, thawed out of module after experiment in vacuum oven and dust condensed on surface of module after experiment in nitrogen environment, it was proven that the condensed dust is indeed ethylene vinyl acetate.

In der vorliegenden Arbeit wurde die heterogen katalysierte Oxidation von Ethen zu Ethylenoxid an Silberkatalysatoren untersucht. Ziel dieser Arbeit war es, Mikrostrukturreaktoren für schnelle und stark exotherme Oxidationsreaktionen zu erproben und diese Epoxidation diente als Modellreaktion. Gleichzeitig wurden explosions- und flammhemmende Eigenschaften des Mikrostrukturreaktors ausgenutzt, um die partielle Oxidation von Ethen zu Ethyenoxid im Explosionsbereich (> 9% Sauerstoff) ohne Sicherheitsprobleme zu ermöglichen. Um die gesteckten Ziele zu erreichen wurden zwei parallele Lösungswege beschritten. Zunächst wurden modulare Mikrostrukturreaktoren und geeignete mikrostrukturierte Katalysatorträger entwickelt, um Untersuchungen verschiedener katalytischer Beschichtungen in dieser neuen und nicht allgemein verfügbaren Reaktorbauweise zu ermöglichen. Zur katalytische Erprobungen dieser Konstruktion war es notwendig, geeignete Beschichtungstechniken zur Immobilisierung katalytisch aktiver Spezies zu entwickeln. Durch die Bauweise dieser Reaktoren als Wandreaktor erschien es anfänglich nicht möglich, kommerziell verfügbare pellet-artige Katalysatoren zu verwenden. Daher wurden, parallel zur Konstruktion der modularen Mikroreaktoren, verschiedene auf Silber basierende Beschichtungstechniken hinsichtlich ihrer Eignung für diese Reaktion erprobt. Zur Erprobung kamen u.a. Silberimmobilisierung in einem durch anodischen Oxidation erzeugen Porensystem bzw. einer durch Sol-Gel Beschichtung erzeugten a-Aluminiumoxid Schicht und die Abscheidung von metallischem Silber per Vakuumbeschichtung auf einem Trägermaterial. Zuletzt wurde die Immobilisierung eines gemahlenen, kommerziellen Katalysators per elektrostatischer Pulverabscheidung auf einem entsprechend präparierten Trägermaterial vorgenommen und erfolgreich erprobt. Die wichtigste Erkenntnis dieser Arbeit aus chemisch-katalytischer Sicht ist der enorm positive Einfluss hoher Sauerstoffkonzentrationen auf die Selektivität und gleichzeitig den Umsatz des umzusetzenden Ethylens. Wird die Sauerstoffkonzentration von unter 10% auf bis zu 80% erhöht, so steigt die Selektivität zu Ethylenoxid um ca. 10% an und simultan kann der Umsatzgrad abhängig vom Katalysator und der Reaktortemperatur um den Faktor 2 bis 10 gesteigert werden. Diese Beobachtung wurde für jeden funktionierenden Katalysator gemacht, unabhängig von dessen Herstellung. Mittels Promotoren wie Cs-Salzen und Stickoxiden konnte die Selektivität in Abwesenheit gängiger Moderatoren wie Chlorkomponenten auf 70% (Cs-Salze) bzw. 75% (NOx) gesteigert werden. Verfahrenstechnisch ist festzuhalten, dass Mikrostrukturreaktoren gleich welcher Bauweise unter allen Reaktionsbedingungen thermisch stabil und beherrschbar blieben. Es wurden Umsatzgrade bis 99% bezüglich Ethen erzielt bzw. Reaktionstemperaturen von über 630 K bei einem binären Ethylen-Sauerstoff Gemisch (20%/80%) angewendet. Angesichts adiabater Temperaturerhöhungen von mehr als 3000 K konnte dennoch ein stabiler Betrieb des Reaktors festgestellt werden. Diese thermische Stabilität war bei Katalysatoren in Festbettreaktoren nicht gegeben.

Title Interaction of Organic Molecules with Metal Passivated Silicon Surfaces Studied via STM Author Petr Zimmermann Department Department of Plasma and Surface Science Supervisor Doc. RNDr. Pavel Sobotík, CSc. Department of Plasma and Surface Science Abstract Organic molecules offer a wide range of optical, electronic or chemical properties. Coupling them to silicon could pave way to novel applications and devices, however, a controlled molecular functionalization of silicon remains challenging due to the presence of highly reactive dangling bonds on its surfaces. We attempt to decrease the reactivity of low index silicon surfaces with an ultra-thin layer of a metal adsorbates and study their interaction with organic molecules via scanning tunnelling microscopy. In the first part we investigate the interaction of ethylene, a small unsaturated molecule, with tin and indium 1D chains grown on Si(001) - 2 × 1. The chains consist of dimers structurally analogous to the dimers of the underlying Si(001) - 2 × 1 surface. Aided by photoelectron spectroscopy we find that the Sn chains are less reactive than the Si(001) surface and that the absence of a π dimer bond renders indium chains inert. In the second part we study the interaction of copper phthalocyanine, a small macrocyclic heteroaromatic compound, with the...

Im Rahmen dieser Arbeit wird ein physikalisches Modell für weichelastische EVA-Schaumstoffe entwickelt, das das mechanische Verformungsverhalten (Spannungs-Verformungs-Kurve) bei der Interaktion zwischen Sportler und Sportgerät am Beispiel eines Laufschuhs anwendungsgerecht – d.h. bei hoher Verformung und Belastungsgeschwindigkeit – kennzeichnet. Im Stand der Technik werden als Einflussfaktoren auf das mechanische Verformungsverhalten von Weichschäumen die Parameter Schaumdichte, Zellgröße bzw. Zelldurchmesser, Schaumhärte und Verformungsgeschwindigkeit ermittelt. Diese werden für die vorliegenden vier Versuchsmaterialien analysiert, wobei die letzten zwei Parameter im Modell Berücksichtigung finden. Das Modell setzt sich aus einem Matrix- und einem Gasphasenanteil zusammen. Der Matrixphasenanteil wird experimentell bei der jeweiligen Verformungsgeschwindigkeit bestimmt, wohingegen der Gasphasenanteil der in den Zellen komprimierten Luft auf einem physikalischen Zusammenhang beruht und anhand der gemessenen Schaumhärte und des Atmosphärendrucks bei der jeweiligen Verformung berechnet wird. Die Voraussetzungen für die Verwendung des Modells, zu denen inkompressible Matrixphase, Geschlossenzelligkeit und keine Querausdehnung des Schaums zählen, werden vorab umfangreich geprüft. Zusammenfassend lässt sich aussagen, dass das gewählte Modell eine gute Übereinstimmung mit den experimentell bestimmten Ergebnissen erzielt. Dies wird anhand der Mittelwertes der Differenz von experimentell ermittelten zu modellierten Daten bestimmt, für den ein Wert von 7 % berechnet wird. / The purpose of this doctoral thesis is developing a physical model for flexible foam materials (e.g. ethylene/vinyl acetate foam) characterizing the mechanical deformation behavior (stress-strain-curve) at the interaction between athlete and sports equipment (e.g. running footwear) during high deformation and high loading rate. Previous studies described various parameters influencing the mechanical deformation behavior of flexible foams: foam density, cell size / cell diameter, foam hardness and loading rate. These parameters are being analyzed for the four present foams whereof the last two parameters were considered in the model. The model consists of a matrix phase measured experimentally at required loading rate multiplied with a correction factor and a gas phase of the air compressed in the foam cells which is calculated by atmospheric pressure and foam hardness. The requirements (incompressible matrix phase, closed cells and zero Poisson ratio) for using the model are verified first of all. In conclusion, the developed model presents a good accordance with the experimental data calculated by a mean difference between experimental and modeled data of 7 %.